Degradation of vinyl ester resin and its composites via cleavage of ester bonds to recycle valuable chemicals and produce polyurethane

[Display omitted] •Vinyl ester resin can be degraded in GVL-H2O solvent with PTSA catalyst.•The ester bonds of vinyl ester resins were cleaved via hydrolysis.•Recycled bisphenol-A diglycidyl ether was cured into polyurethane.•Amphiphilic PTSA catalyst facilitates itself entrancing into the matrix of VER. Vinyl ester resins (VER) and its composites are widely used in chemical industry and municipal engineering. However, its dense three-dimensional network structure makes its degradation and recycling a great challenge. Herein, a novel, efficient and green degradation system gamma-valerolactone (GVL)–H2O/p-toluene sulfonic (PTSA) was developed to degrade VER and its composites. VER was completely degraded in the GVL-H2O/PTSA at 210 °C and 0.6 MPa. By combing SEM-EDS, IR, NMR, GPC and MALDI-TOF-MS analysis, it was clarified that VER swelled well in GVL, allowing the transfer of PTSA and H2O through the resin matrix. The ester bonds in VER were cleaved via hydrolysis with H2O catalyzed by the sulfonic acid of PTSA, and high value-added polymer products, i.e., copolymer of styrene and methacrylic acid (SMAA) and bisphenol-A diglycidyl ether (DGEBA), were recycled, which accounted for ca. 87.0 wt% of raw VER. DGEBA can be recycled to prepare a new PU material. The GVL-H2O/PTSA system was also effective for degrading UPR and VER-containing composites. This work provides a practical strategy for chemical degradation and recovery of thermoset VER resins.